CN101104137A - Method for preparing polypyrole-polycarbonate composite membrane fixed and carried cibacron blue - Google Patents
Method for preparing polypyrole-polycarbonate composite membrane fixed and carried cibacron blue Download PDFInfo
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- CN101104137A CN101104137A CNA2007100093241A CN200710009324A CN101104137A CN 101104137 A CN101104137 A CN 101104137A CN A2007100093241 A CNA2007100093241 A CN A2007100093241A CN 200710009324 A CN200710009324 A CN 200710009324A CN 101104137 A CN101104137 A CN 101104137A
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Abstract
Disclosed is a preparation method of the poly pyrrole-polycarbonate composite membrane of the supported Cibacron Blue, which relates to the preparation technique of the affinity membrane used for the separation and purification of the protein, the invention provides the preparation method of the poly pyrrole-polycarbonate composite membrane of the supported Cibacron Blue having good hydrophilic property and excellent biocompatibility. The invention takes the polycarbonate membrane as the basement membrane, the basement membrane is fixed in the middle of the diffusion pool containing double pools after the pretreatment in the Cibacron Blue solution; the oxidant and pyrrole monomer solution are respectively added into each pool of the diffusion pool that contains two pools; the active ligand Cibacron Blue is added into any pool of the diffusion pool with the reaction temperature being controlled between 0-40 DEG C and the reaction time is 0.5-8h; finally the poly pyrrole-polycarbonate composite membrane of the supported active ligand Cibacron Blue can be obtained after the cleaning treatment of the basement membrane when the reaction finishes. The prepared affinity membrane has great chemical durability, hydrophilic property and excellent biocompatibility. The composite membrane can be used for separation and purification of protein.
Description
Technical field
The present invention relates to a kind of technology of preparing of affinity membrane of the separation and purification that is used for protein, especially relate to the preparation method of the polypyrole-polycarbonate composite membrane of a kind of immobilized hot Ba Lan.
Background technology
Along with bioengineering and development of life science, more and more higher requirement has been proposed for the purifies and separates of large biological molecules such as albumen, polypeptide, enzyme.Although adopt traditional separation method, can make product purity obtain to improve as precipitation, crystallization, film separation, chromatography etc., under many circumstances, exist problems such as technology is loaded down with trivial details, activity recovery is low, purification effect is undesirable.The affinity membrane technology that development in recent years is got up has been showed good prospects for application in the separation and purification field of protein, and has obtained many practical applications.So-called affinity membrane technology is film to be separated with affinity chromatography combine, and makes it to have concurrently both characteristics.When feed liquid under certain pressure with convection type when the fenestra, object in the solution can be diffused on the dentate soon, and then the generation specificity interacts, object is retained on the film, and then the object that will be retained on the film by eluent disintegrates down from film, thereby reaches the purpose with other separating substances.Separate with traditional film, affinity chromatography compares; the affinity membrane separation not only has purifying multiple height, pressure drop is little, disengaging time is short, large biological molecule probability of sex change in separation is little; allow characteristics such as charging rate faster, and than the easier realization scale of post affinity chromatography purifies and separates.
Affinity membrane separates employed filter membrane should have good chemical stability, excellent in chemical reactivity worth and excellent biological compatibility energy.Chinese patent CN02130926.4, CN02130927.2, the compound asymmetric milipore filter of the disclosed compatibility polysulfones-hydroxyethylcellulose of CN02153350.4, the compound asymmetric milipore filter of compatibility polysulfone-chitosan and the three kinds of affinity membranes such as nylon-chitosan complex film that are used for affine micro-filtration have advantages such as dentate supported quantity height, good biocompatibility, non-specific adsorption be low.
Polycarbonate membrane is a kind of track miillpore filter, have aperture evenly (pore size and density are controlled easily), pliability and mechanical strength is good, good chemical stability, but this film lacks active function groups, must carry out the requirement that modification could be satisfied affine separation to it.
Summary of the invention
Purpose of the present invention aims to provide the preparation method of the polypyrole-polycarbonate composite membrane of a kind of immobilized hot Ba Lan with good hydrophilicity energy and good biocompatibility.
The present invention is realized by the following technical programs:
1) with the polycarbonate membrane is basement membrane, basement membrane is carried out preliminary treatment in hot Ba Lan solution;
2) pretreated basement membrane is fixed in the middle of the diffusion cell that contains two ponds;
3) oxidant and pyrrole monomer solution are added respectively in two ponds of diffusion cell;
4) the hot Ba Lan of active dentate is added in arbitrary pond of diffusion cell, 0～40 ℃ of control reaction temperature, reaction time 0.5～8h, solution in two ponds carries out the concurrent living oxidative polymerization of phase counterdiffusion by film, the polypyrrole that generates through chemical oxidation deposits on the surface and hole wall of basement membrane, and the hot Ba Lan of active dentate is entrained in the polypyrrole molecule by ionic bond;
5) reaction finishes back taking-up basement membrane through cleaning treatment, obtains the immobilized polypyrole-polycarbonate composite membrane that the hot Ba Lan of active dentate is arranged at last.
The aperture of polycarbonate membrane is preferably 0.05～8 μ m.Basement membrane is carried out preliminary treatment for placing hot Ba Lan solution to vacuumize the basement membrane or with filter suction filtration suffering Ba Lan solution or place hot Ba Lan solution to leave standstill DIFFUSION TREATMENT in hot Ba Lan solution.
Pyrrole monomer solution is the aqueous solution of 5～120mmol/L.
Oxidant is ammonium persulfate aqueous solution or the ferric chloride aqueous solutions of 200～400mmol/L or the hydrogenperoxide steam generator of pH2 of 10～40mmo1/L.The mol ratio of pyrrole monomer and oxidant is 1: (1～5).
Hot Ba Lan concentration is 0.1～1.0mmol/L.The mol ratio of pyrrole monomer and Xin Balan is (15～250): 1.The control reaction temperature is preferably 4～10 ℃, and the reaction time is preferably 1～2.5h.
The present invention as dentate, is a basement membrane with the polycarbonate membrane with hot Ba Lan, by polypyrrole it is carried out modification.The hot Ba Lan of the dentate selected for use is a kind of reactive dye, and this dyestuff and protein have good binding specificity, and has good stability, low price, is easy to prepare and advantages such as storage; And polypyrrole has the doping/dedoping characteristic of completely reversibility, utilizes this characteristic can realize the immobilized of dentate or replacing, and in addition, polypyrrole also has excellent biological compatibility, chemical stability and electric conductivity are arranged.Immobilized on the prepared composite membrane of the present invention have the active dentate-Xin Ba indigo plant that links to each other with polypyrrole layer by ionic bond, compare with the preparation method of common affinity membrane, the immobilized dentate of this method is easy and simple to handle, and having unique replacing dentate function, prepared affinity membrane has good chemical stability, hydrophily and good biocompatibility.This composite membrane can be used for the separation and purification of protein.
Description of drawings
Fig. 1 is the diffusion cell structural representation of the embodiment of the invention.
Fig. 2 is the stereoscan photograph on the embodiment of the invention 1 selected basement membrane-polycarbonate membrane surface.
Fig. 3 is the stereoscan photograph on the polypyrole-polycarbonate composite membrane surface of the prepared immobilized hot Ba Lan of the embodiment of the invention 1
Fig. 4 removes the profile scanning electromicroscopic photograph of sample behind the basement membrane for the polypyrole-polycarbonate composite membrane of the prepared immobilized Xin Balan of having of the embodiment of the invention 1 is molten.
Fig. 5 goes the infrared spectrogram of sample behind the basement membrane for the polypyrole-polycarbonate composite membrane of the prepared immobilized Xin Balan of having of the embodiment of the invention 1 is molten.In Fig. 5, abscissa is wave number Wavenumbers (cm
-1), ordinate is percentage transmission Transmittance (%), curve 1: Xin Balan, curve 2: the polypyrrole of the hot Ba Lan that mixes, curve 3: polypyrrole.
The specific embodiment
The invention will be further described below by specific embodiment.
1) preliminary treatment of basement membrane:
Getting an aperture is the polycarbonate membrane of 0.8 μ m, thickness 20 μ m, diameter 25mm, is dipped in volume and is 30mL, concentration and be 30min in the hot Ba Lan aqueous solution of 0.2mmol/L, then film is placed filter with the hot Ba Lan solution of the 0.2mmol/L suction filtration of 30mL 5 times.
2) oxide deposition of the doping of dentate and polypyrrole:
Get poly-1 basement membrane of handling well 3 of step and be fixed in the middle (see figure 1) of the diffusion cell device that has two ponds 1 and 2, add the ammonium persulfate aqueous solution 30mL of 30mmol/L in the pond 1 of diffusion cell; 2 add the mixed solution 30mL that contains hot Ba Lan and pyrrole monomer in the pond, and the concentration of hot Ba Lan is 0.2mmol/L in the pond 2, and the concentration of pyrrole monomer is 15mmol/L.React 2.5h down at 4 ℃.
3) cleaning of film, preservation:
Be reacted to the solution of pouring out after time of setting in two ponds, take out the composite membrane of step 2 preparation, wash repeatedly with distilled water at once, room temperature is placed and is dried, and promptly obtains the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan.
By comparison diagram 2 and Fig. 3 as can be seen: (1) because prepared composite membrane is to have covered one deck polypyrrole on the surface of basement membrane and hole wall, the aperture of composite membrane is less than the aperture of basement membrane; (2) because polypyrrole is a black, the composite membrane color that is obtained is deeper than former basement membrane; (3) prepared polypyrole-polycarbonate composite membrane surface is even, and form is good.
The composite membrane of Fig. 4 is molten go behind the basement membrane profile scanning electromicroscopic photograph of sample show with basement membrane-polycarbonate membrane is molten go after, obtained the porous polypyrrole film with former basement membrane complementation, proved that further formed polypyrrole layer is complete, covered on the surface and hole wall of polycarbonate membrane uniformly.And can see from infrared spectrogram (Fig. 5): the polypyrrole (mark 2) of the hot Ba Lan of (1) doping and polypyrrole (mark 3) are at 1631cm
-1, 1384cm
-1, 1091cm
-1, 1047cm
-1Characteristic absorption peak is all arranged, belong to characteristic absorption for pyrrole ring; (2) polypyrrole (mark 2) of the hot Ba Lan of doping and Xin Balan (mark 1) are then at 1560cm
-1, 1221cm
-1, 1190cm
-1The position have identical absworption peak, belong to one of characteristic absorption peak for hot Ba Lan; (3) polypyrrole of the hot Ba Lan of doping, Xin Balan, polypyrrole are at 3400cm
-1About absworption peak is all arranged, belong to stretching vibration peak for N-H, C-H, illustrate in the polypyrrole, Xin Balan, polypyrrole structure of the hot Ba Lan that mixes all to have N-H, C-H structure; The above analysis confirms that prepared polypyrole-polycarbonate composite membrane is immobilized a Xin Balan.
1) preliminary treatment of basement membrane:
Getting an aperture is the polycarbonate membrane of 0.2 μ m, thickness 20 μ m, diameter 25mm, is fixed in the middle of the diffusion cell device, adds the hot Ba Lan aqueous solution 30mL of 0.4mmol/L in pond 1, leaves standstill 2h and makes Xin Balan diffuse through basement membrane.
2) oxide deposition of the doping of dentate and polypyrrole:
Pour out the hot Ba Lan aqueous solution in the step poly-1, in pond 1, add 300mmol/L ferric chloride aqueous solutions 30mL then; Add the mixed solution 30mL that contains hot Ba Lan and pyrrole monomer in pond 2, the concentration of hot Ba Lan is 0.4mmol/L in the pond 2, and the concentration of pyrrole monomer is 100mmol/L.React 30min down at 0 ℃.
3) cleaning of film, preservation:
Method according to embodiment 1 is cleaned, is preserved, and promptly obtains the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan.
1) preliminary treatment of basement membrane:
Getting an aperture is the polycarbonate membrane of 3 μ m, thickness 20 μ m, diameter 25mm, places a device that can airtightly vacuumize, and adding 30mL concentration is the hot Ba Lan aqueous solution of 0.6mmol/L, makes the vacuum of device keep 20min under 30kPa by vavuum pump.
2) oxide deposition of the doping of dentate and polypyrrole:
Take out poly-1 basement membrane of handling well of step and be fixed in the middle of the diffusion cell device, in the pond 1 of diffusion cell, add the aqueous hydrogen peroxide solution 30mL of pH2; Add the mixed solution 30mL that contains hot Ba Lan and pyrrole monomer in pond 2, the concentration of hot Ba Lan is 0.6mmol/L in the pond 2, and the concentration of pyrrole monomer is 15mmol/L.React 4h down at 0 ℃.
3) cleaning of film, preservation:
Method according to embodiment 1 is cleaned, is preserved, and promptly obtains polypyrrole-carbonic ester composite membrane of immobilized hot Ba Lan.
Embodiment 4
1) preliminary treatment of basement membrane:
Getting an aperture is the polycarbonate membrane of 0.2 μ m, thickness 20 μ m, diameter 25mm, according to the preprocess method of basement membrane among the embodiment 3 basement membrane is carried out preliminary treatment.
2) oxide deposition of the doping of dentate and polypyrrole:
Take out poly-1 basement membrane of handling well of step and be fixed in the middle of the diffusion cell device, add the mixed solution 30mL that contains hot Ba Lan and ammonium persulfate in the pond 1 of diffusion cell, the concentration of hot Ba Lan is 0.4mmol/L in the pond 1, and the concentration of ammonium persulfate is 30mmol/L; The aqueous solution 30mL that in pond 2, adds the 7.5mmol/L pyrrole monomer.React 2h down at 10 ℃.
3) cleaning of film, preservation:
Method according to embodiment 1 is cleaned, is preserved, and promptly obtains polypyrrole-carbonic ester composite membrane of immobilized hot Ba Lan.
Claims (9)
1. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan is characterized in that its step is as follows:
1) with the polycarbonate membrane is basement membrane, basement membrane is carried out preliminary treatment in hot Ba Lan solution;
2) pretreated basement membrane is fixed in the middle of the diffusion cell that contains two ponds;
3) oxidant and pyrrole monomer solution are added respectively in two ponds of diffusion cell;
4) the hot Ba Lan of active dentate is added in arbitrary pond of diffusion cell, 0～40 ℃ of control reaction temperature, reaction time 0.5～8h, solution in two ponds carries out the concurrent living oxidative polymerization of phase counterdiffusion by film, the polypyrrole that generates through chemical oxidation deposits on the surface and hole wall of basement membrane, and the hot Ba Lan of active dentate is entrained in the polypyrrole molecule by ionic bond;
5) reaction finishes back taking-up basement membrane through cleaning treatment, obtains the immobilized polypyrole-polycarbonate composite membrane that the hot Ba Lan of active dentate is arranged at last.
2. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan as claimed in claim 1, the aperture that it is characterized in that polycarbonate membrane is 0.05～8 μ m.
3. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan as claimed in claim 1 is characterized in that basement membrane is carried out preliminary treatment for placing hot Ba Lan solution to vacuumize basement membrane or with filter suction filtration suffering Ba Lan solution or place hot Ba Lan solution to leave standstill DIFFUSION TREATMENT in hot Ba Lan solution.
4. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan as claimed in claim 1 is characterized in that pyrrole monomer solution is the aqueous solution of 5～120mmol/L.
5. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan as claimed in claim 1 is characterized in that oxidant is ammonium persulfate aqueous solution or the ferric chloride aqueous solutions of 200～400mmol/L or the hydrogenperoxide steam generator of pH2 of 10～40mmol/L.
6. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan as claimed in claim 1, the mol ratio that it is characterized in that pyrrole monomer and oxidant is 1: 1～5.
7. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan as claimed in claim 1 is characterized in that hot Ba Lan concentration is 0.1～1.0mmol/L.
8. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan as claimed in claim 1, the mol ratio that it is characterized in that pyrrole monomer and Xin Balan is 15～250: 1.
9. the preparation method of the polypyrole-polycarbonate composite membrane of immobilized hot Ba Lan as claimed in claim 1 is characterized in that 4～10 ℃ of reaction temperatures, reaction time 1～2.5h.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100093241A CN100531872C (en) | 2007-08-03 | 2007-08-03 | Method for preparing polypyrole-polycarbonate composite membrane of fixed load cibacron blue |
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| CNB2007100093241A CN100531872C (en) | 2007-08-03 | 2007-08-03 | Method for preparing polypyrole-polycarbonate composite membrane of fixed load cibacron blue |
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| CN101104137A true CN101104137A (en) | 2008-01-16 |
| CN100531872C CN100531872C (en) | 2009-08-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597565A (en) * | 2016-03-11 | 2016-05-25 | 天津工业大学 | Polytetrafluoroethylene electro-catalysis porous membrane and preparing method thereof |
| CN110237713A (en) * | 2019-07-04 | 2019-09-17 | 中国科学院生态环境研究中心 | A kind of electroresponse polymer film and preparation method thereof, application method and purposes |
| CN112588127A (en) * | 2020-12-31 | 2021-04-02 | 杭州高通膜技术有限公司 | Method for modifying polymer porous membrane through diffusion reaction |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310688A (en) * | 1988-10-31 | 1994-05-10 | Sepracor Inc. | Method and apparatus for eluting proteins in affinity membrane process |
| CN1167494C (en) * | 2002-09-17 | 2004-09-22 | 天津大学 | Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film |
| CN1189236C (en) * | 2002-09-17 | 2005-02-16 | 天津大学 | Preparation method of nylon-shell glycan compound film for affinity microfilter |
| CN1159092C (en) * | 2002-11-29 | 2004-07-28 | 天津大学 | Prepn precess of composite asymmetrical affinity polysulfone-hydroxyethyl cellulose ultrafiltering film |
| CN100446844C (en) * | 2006-09-15 | 2008-12-31 | 东华大学 | Nylon affinity membrane preparing method and use |
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2007
- 2007-08-03 CN CNB2007100093241A patent/CN100531872C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597565A (en) * | 2016-03-11 | 2016-05-25 | 天津工业大学 | Polytetrafluoroethylene electro-catalysis porous membrane and preparing method thereof |
| CN105597565B (en) * | 2016-03-11 | 2018-02-27 | 天津工业大学 | Polytetrafluoroethylene (PTFE) electro-catalysis perforated membrane and preparation method thereof |
| CN110237713A (en) * | 2019-07-04 | 2019-09-17 | 中国科学院生态环境研究中心 | A kind of electroresponse polymer film and preparation method thereof, application method and purposes |
| CN112588127A (en) * | 2020-12-31 | 2021-04-02 | 杭州高通膜技术有限公司 | Method for modifying polymer porous membrane through diffusion reaction |
| CN112588127B (en) * | 2020-12-31 | 2022-03-22 | 杭州高通膜技术有限公司 | Method for modifying polymer porous membrane through diffusion reaction |
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